Process for hydrogenating distillable carbonaceous materials



1937- M. PIER ET AL.

PROCESS FOR HYDROGENATING DISTILLABLE CARBONACEOUS MATERIALS Filed Dec. 22, 1932 PR E'HEA TER HIGH PRESS URE wsss E1.

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Patented Nov. 9, 1937 PROCESS FOR HYDROGENATIN G DISTILLA- BLE CARBONACEOUS MATERIALS Mathias Pier, Heidelberg, and Walter Simon and Walter Kroenig, Ludwigshafen-on-the- Rhine, Germany; assignors to Standard-I. G. Company, Linden, N. 3., a corporation of Delaware Application December 22, 1932, Serial No. 648,436

In Germany January 2, 1932 Y 3 Claims.

This invention is concerned with the treatment with hydrogenating gases of distillable carbonaceous materials.

the present invention.

It has already been proposed in the production of valuable hydrocarbon products, and in particular those of low boiling point, by destructive hydrogenation of distillable carbonaceous materials,

by treatment with hydrogen or gases containing hydrogen at temperatures above 300 C. and under elevated presume, to work in contact with catalysts containing halogens in a free or combined state.

pounds themselves have a very considerable catalytic activity.

Improved results are however usually obtained by employing the said iodine compounds simultaneously with other compounds of metals of the second to the eighth group of the periodic systern or mixtures of these, and more particularly 35 the oxides, hydroxides or sulphides of the said metals. Especially good results are obtained with V the compounds of metals of the groups 5 and 6 of the periodic system. The addition of other compounds of heavy metals as for example com- 40 pounds of copper, silver, zinc, tin, cadmium, manganese, uranium, rhenium and especially nickel or cobalt and more particularly the oxides, hy-

droxides, sulphides or carbonates of said heavy metals give very good results. Compounds such 45 as oxides, hydroxides, sulphides or carbonates of lithium, magnesium or aluminium may also be employed. Elementary silicon or compounds thereof may also be present.

The nitrides, phosphides, borides, arsenides an 50 selenides of the metals of groups 2 to 8 of the periodic system also form suitable additions.

Particularly good results are obtained by employing the said iodine compounds in conjunction with sulphides of metals of group 5 or 6 55 of the periodic system or of nickel or cobalt.

The drawing is a diagrammatic sketch in e1e-' 5 vation of an apparatus adapted for carrying out When working with an addition of the said metal sulphides the aforesaid iodine compounds may be replaced by halogen compounds other than compounds of iodine as for example the compounds of bromine or chlorine of the said metals silver, copper, titanium, tin, manganese, nickel or cobalt or mixtures thereof. In this case the halogen-compounds of chromium may also be employed.

Carrier substances or substances having a dispersing action, and which sometimes also have a catalytic action for example active carbon, silica gel, pumice stone or porous sherds of burned fire clay may also be employed.

About 0.01 to 10% by weight of said halogen compound may be added to the initial materials. When treating coal pastes or hydrocarbons of .high boiling point which are passed out of the reaction vessel together with the reaction products, preferably an amount of catalyst of between 0.01 and 5% by weight is employed, whereas in the treatment of liquid hydrocarbon initial materials of high boiling point when the benzine and middle oil fractions distil ofi from the reaction vessel whilst the higher boiling products remain therein, it may be advantageous to work with a higher concentration of catalyst.

As initial materials for treatment in accordance with the present invention may be employed coals of all varieties such as pit coal or brown coal, as such or made into a paste or suspension in oil, shale, peat, tars, mineral oils, shale oils or the distillation, conversion or extraction products from the same, as for example, products obtained by cracking or destructive hydrogenation. Good results are also obtained by the process according to the present invention in the destructive hydrogenation of asphalts or resins.

The catalysts in accordance with the present invention may be employed when working in the liquid, gaseous or solid phase.

The catalyst may be introduced into the re' action vessel at any suitable point. Thus it may be mixed with the initial materials prior to their introduction into the preheating zone, where such is employed, or only after preheating, or the catalyst may be introduced directly into the reaction vessel. If desired, and more particularly when working in the gaseous phase, the reaction vessel may be packed with catalyst or the catalyst may be arranged on suitable supports in the reaction vessel, which may if desired be movable. In this case it is not essential also to mix catalyst with the initial materials.

The catalyst may, if

desired, be wholly or in part employed in a finely ground state, the g'rinding being even carried down to colloidal dimensions. Solid carbonaceous initial materials may be impregnated with a solution of the catalytic material.

The expression treatment with hydrogenating gases of distillable carbonaceous materials" is intended to comprise the most varied reactions, and the catalysts employed in accordance with the present invention have been found to be particularly advantageous in all of these said reactions. Thus the expression includes more particularly the destructive hydrogenation of carbonaceous materials, such as coal of all varieties, including lignite, other solid carbonaceous materials such as peat, shales and wood, or mineral oils, tars and the distillation, conversion and extraction products thereof, to produce hydrocarbons of all sorts, such as motor fuels andin particular anti-knock motor fuels, middle oils, kerosene and lubricating oils. The said expression also includes the removal of non-hydrocarbon impurities, such as sulphur or oxygen-containing subtances or nitrogen compoundsby the action of hydrogen or gases containing or supplying hydrogen from crude carbonaceous materials, for example the refining by treatment with hydrogen of crude benzol, of

crude motor fuels or of lubricating oils. The said expression further includes the conversion of oxygen or sulphur containing organic compounds to produce the corresponding hydrocarbons or hydrogenated hydrocarbons, for example, the conversion of phenols or cresols into the corresponding cyclic hydrocarbons or hydrogenation products thereof. Finally it includes the hydrogenatiorr of unsaturated compounds and more particularly of unsaturated hydrocarbons or 01 aromatic compounds and more particularly of aromatic hydrocarbons, for example, to produce hydroaromatic hydrocarbons.

The said reactions with hydrogen or hydrogen containing gases are usually carried out at temperatures between 250 and 700 C. and as a rule between 380 and 550 C. The pressures employed are usually in excess of 20 atmospheres and as a rule preferably in excess of 50 atmospheres. In some reactions however, for example in the refining of crude benzol, rather low pressures, for example of the order of 40 atmospheres may be employed. Generally however pressures of about 100, 200, 300, 500 and in some cases even 1000 atmospheres come into question.

The amount of hydrogen maintained in the reaction space, and parts connected therewith, if any, varies greatly with the nature of the particular initial materials treated or according to the result in view. In general 400, 600, 1000 cubic meters or more of hydrogen measured under normal conditions of temperature and pressure, per

ton ot' carbonace'ous material treated may be used.

The gases for'use in the reaction may consist of hydrogen alone or of mixtures containing hy-v drogen (for example a mixture of hydrogen with nitrogen or for example water gas) or of hydrogen mixed with carbon dioxide, sulphuretted hydrogen, water vapour or methane or other hydrocarbons. Or the hydrogen may be generated in the reaction chamber by the interaction of water arid coal, carbon monoxide, hydrocarbons and the 11 e.

It is particularly advantageous to operate by continuously introducing fresh carbonaceous material into the reaction vessel and to continuously remove products therefrom. If desired several reaction vessels may be employed in which different conditions of temperature and/or pressure may, if necessary, be maintained and in which different catalysts may also be employed. sufliciently converted reaction products may be removed after any of the reaction vessels. Materials which have not been sufliciently reacted on may be recycled or treated in a further reaction vessel.

The benzines obtained according to the present process when working in the vapour phase are usually characterized by the feature that the fraction thereof boiling between and 190 C. has a particularly low content in hydrogen whereas, as a general rule, it is just this fraction of the benzine which particularly gives rise to knocking when it is employed as a fuel in internal combustion engines. In addition to such benzine a middle oil rich in hydrogen is usually obtained, which may be employed'directly as an illuminating oil or as a Diesel oil, or which may be converted into benzine by cracking or a further destructive hydrogenation.

. In the drawing 'numeral I designates a feed tank from which the oilis withdrawn by a pipe 2 and is forced by pump 3 through a heat exchanger 4. Hydrogen gas is introduced by a line 5 and directly mixes with the oil prior to the entrance into heat exchanger 4. The mixture of oil and hydrogen then passes by a line 6 into a preheater 1 preferably in the form of a coil and thence by a line 8 into a high pressure reaction vessel 9 which is adapted to withstand the pressure and temperature conditions and is packed with a catalyst shown generally-at l0. The reaction products pass from the-oven by a line H through heat exchanger 4 and into a cooler l2.

The cooled product discharges into a separator B from which the liquefied portions are withdrawn by pipe I, the gas by a pipe IS. The gas may be recirculated by a pump l6, mixing with Example 1 From the benzine which has been produced from mineral oil by distillation, a fraction is distilled boiling between and C. and this is passed together with hydrogen at a temperature of 550 C. and under a pressure of 200 atmospheres over a catalyst prepared from a mixture of molybdic acid, zinc oxide and silver iodide, titanium iodide or nickel iodide, the partial pressure of the improved product being maintained at about 30 atmospheres.

A reaction product rich in aromatic hydrocarbons and boiling'below C. is obtained. If this product be mixed with a benzine which when used by itself in an internal combustion engine with a, high compression ratio has a tendency to knock, a blended fuel is obtained which is entirely free from these tendencies.

Example 2 temperature of 410 C. with 30 parts by weight 75 of manganese bromide. Over this catalyst a middle oil distilled from mineral oil is passed in the vaporous phase together with hydrogen at a temperature of 440 C. and under a pressure of 200 atm. The product contains 60% of henzine, which has a knock rating correspondingto that of a mixture of about 69 parts of iso-octane and 31 parts of normal pentane. The middle oil is very rich in hydrogen so that it can be em ployed directly as an illuminating oil.

If manganese bromide is not added to the tungsten sulphide a benzine is obtained which has a knock rating corresponding to a mixture of 63 parts 01- iso-octane with 3'7 parts of normal pentane. In place of manganese bromide, titanium bromide, cobalt chloride, chromium bromide, copper iodide or an amount of 5 per cent of tin iodide may be added to the tungsten sulphide.

In place of the above mentioned mixtures pieces of pressed tungsten sulphide maybe rigidly arranged in the reaction vessel besides pieces of any of the said halogen compounds.

Example 3 Pit coal is finely ground and mixed with 50% of its weight of a heavy oil obtained by the destructive hydrogenation of the said coal- To this mixture 2% based on the weight of coal of tin iodate is added. This mixture is then spread in the form of a thin layer on plate-like insertions in a high pressure reaction vessel and is heated for 3 hours to a. temperature of about 450 C.

' in a current of streaming hydrogen under a pressure of 250 atmospheres, 93% of the coal is thus converted into valuable for the most part liquid products which contain less than 5% of asphalt, In place of the said catalyst cobalt iodide or manganese iodide may be employed.

Example 4 .4 residue boiling above 325 c. obtained from mineral oils is mixed with 5% 0! its weight or tin iodide, and is heated in an autoclave for a atmospheres. The reaction product on distilla-- tion yields of an. overhead consisting of benzine and gas oil and 55% of a distillation residue On subjecting the residue to dewaxlng treatment a lubricating oil is obtained having a viscosity of 5.4 Engler at C., a specific gravityof 0.898, a flat temperature viscosity curve and a green colour. By a mere distillation of the residual oil employed as the initial material it is impossible to obtain oil from which by simple dewaxing a lubricating oil can be obtained, since this has too high a content of asphalt.

In our copending application Ser. No. 648,435, now Patent No. 2,028,348, we have claimed a process in which distillable carbonaceous mate rials are hydrogenated in the presence of molybdenum bromide and tungsten sulfide.

What weclaim is:

1. A process for the treatment with a hydrogenating gas of a distillable carbonaceous material which comprises treating thesaid carbonaceous material with the said gas at a temperature between 250 and 700 C. and under pressure of at least 20 atmospheres while in contact with a catalyst comprising a mixture of tungsten sulphide and manganese bromide.

2. The process of destructively hydrogenating a middle oil which comprises subjecting said oil to the action of hydrogen at a temperature of about 440 C. and under a pressure of 200'atmospheres in the presence of a catalyst consisting of tungsten sulphide and manganese bromide.

, 3. The processas defined in claim 2 wherein the conversion is conducted in the vapor phase.

WALTER .SIMON. WALTER KROENIG. 

